The problem of retrieving minor concentrations of constituents by ground-based Fourier-transform infrared emission spectroscopy is addressed by means of the concept of differential optical emission spectroscopy in analogy to the concept of differential optical absorption spectroscopy. Using the prominent ν 3 ozone feature at 1043 cm-1, we show that the strength of the spectral signature depends not only on the amount of ozone but also on the atmospheric thermal structure. This dependence can be described by a rather accurate approximation, which was used to construct a simple diagram to estimate the amount of column ozone between the instrument site and a cloud deck as well as to determine the detection limit. The detection limit is shown to depend on cloud base height. For a given thermal lapse rate it was found that the lower the detection limit, the higher the cloud base altitude. However, as shown in a case study with variable cloud base height, the concept fails for semitransparent clouds. Multiple scattering of the emitted radiation within the clouds yielded a path enhancement that simulated an enhanced amount of constituent. The path enhancement was estimated to be 2.4–4 km at 1000 cm-1 for low-level clouds, equivalent to an enhancement factor of 6–21. The multiple scattering effect has considerable consequences for ground-based as well as for nadir satellite retrieval techniques in cloudy skies.
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